Method for producing compound containing BIS (perfluoroalkylsulfonyl) methyl group and salt thereof, and solid electrolyte membrane produced using same

Abstract

A method for producing compounds containing a bis(perfluoroalkylsulfonyl)methyl group or salts thereof, wherein the compounds have high acidity and hydrophobicity and are useful as raw material compounds for a resin.

The invention claimed is: 
     
       1. A method for producing a compound represented by general formula (5), comprising:
 initiating dehydration condensation between a compound represented by general formula (1) and an aldehyde compound represented by general formula (2) or an acetal compound represented by general formula (3); and then 
 causing reduction with a hydrosilane compound represented by general formula (4); 
 
       
         
           
           
               
               
           
         
         wherein Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms, 
         A represents a monovalent organic group, 
         Y represents a single bond or a substituted or unsubstituted C 1 -C 4  linear alkylene group, a substituted or unsubstituted C 3 -C 4  branched alkylene group, or a substituted or unsubstituted C 3 -C 4  cyclic alkylene group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group comprises an ether bond or an ester bond; 
         R 1  and R 2  mutually independently represent a C 1 -C 12  linear alkyl group, a C 3 -C 12  branched alkyl group, or a C 6 -C 12  cyclic alkyl group; and 
         R 3  to R 5  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 8  linear alkyl group, a substituted or unsubstituted C 3 -C 8  branched alkyl group, a substituted or unsubstituted C 6 -C 8  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 8  aryl group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 8  linear alkyl group, substituted C 3 -C 8  branched alkyl group, substituted C 6 -C 8  cyclic alkyl group, and substituted C 6 -C 8  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 8  linear alkyl group, substituted C 3 -C 8  branched alkyl group, substituted C 6 -C 8  cyclic alkyl group and substituted C 6 -C 8  aryl group comprises an ether bond or an ester bond. 
       
     
     
       2. A production method as claimed in  claim 1 , wherein the organic group A is a monovalent organic group represented by general formula (6), general formula (7), general formula (8) or general formula (9): 
       
         
           
           
               
               
           
         
         wherein R 6  to R 15  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond or an ester bond, and 
         R 6  to R 8  are bonded to form a cyclic structure; 
         X represents CH 2 , C(CH 3 ) 2  or an oxygen atom; 
         R 16  mutually independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a sulfonic acid group, a cyano group, a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond, an ester bond or a sulfonyl group; 
         l is an integer between 0 and 2; and 
         m is an integer between 0 and 5. 
       
     
     
       3. A compound represented by general formula (5) 
       
         
           
           
               
               
           
         
         wherein A represents a monovalent organic group represented by general formula (8): 
       
       
         
           
           
               
               
           
         
         wherein R 9  to R 15  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond or an ester bond; 
         X represents CH 2 , C(CH 3 ) 2  or an oxygen atom; 
         Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms, and 
         Y represents a single bond or a substituted or unsubstituted C 1 -C 4  linear alkylene group, a substituted or unsubstituted C 3 -C 4  branched alkylene group, or a substituted or unsubstituted C 3 -C 4  cyclic alkylene group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group comprises an ether bond or an ester bond. 
       
     
     
       4. A method for producing a salt represented by general formula (12), 
       
         
           
           
               
               
           
         
         comprising: 
         (a) initiating dehydration condensation between a compound represented by general formula (1) and an aldehyde compound represented by general formula (2) or an acetal compound represented by general formula (3); 
         (b) causing reduction with a hydrosilane compound represented by general formula (4); 
       
       
         
           
           
               
               
           
         
         wherein Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms, 
         A represents a monovalent organic group, 
         Y represents a single bond or a substituted or unsubstituted C 1 -C 4  linear alkylene group, a substituted or unsubstituted C 3 -C 4  branched alkylene group, or a substituted or unsubstituted C 3 -C 4  cyclic alkylene group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group comprises an ether bond or an ester bond; 
         R 1  and R 2  mutually independently represent a C 1 -C 12  linear alkyl group, a C 3 -C 12  branched alkyl group, or a C 6 -C 12  cyclic alkyl group; and 
         R 3  to R 5  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 8  linear alkyl group, a substituted or unsubstituted C 3 -C 8  branched alkyl group, a substituted or unsubstituted C 6 -C 8  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 8  aryl group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 8  linear alkyl group, substituted C 3 -C 8  branched alkyl group, substituted C 6 -C 8  cyclic alkyl group, and substituted C 6 -C 8  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 8  linear alkyl group, substituted C 3 -C 8  branched alkyl group, substituted C 6 -C 8  cyclic alkyl group, and substituted C 6 -C 8  aryl group comprises an ether bond or an ester bond; and 
         (c) causing a neutralization reaction of a compound represented by general formula (5) with an alkali metal salt, 
         wherein Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms; 
         A represents a monovalent organic group; 
         Y represents a single bond or a substituted or unsubstituted C 1 -C 4  linear alkylene group, a substituted or unsubstituted C 3 -C 4  branched alkylene group, or a substituted or unsubstituted C 3 -C 4  cyclic alkylene group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group comprises an ether bond or an ester bond; and 
         M represents an alkali metal ion or an ammonium ion. 
       
     
     
       5. A method for producing a salt, as claimed in  claim 4 , wherein the organic group A is a monovalent organic group represented by general formula (6), general formula (7), general formula (8) or general formula (9): 
       
         
           
           
               
               
           
         
         wherein R 6  to R 15  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond or an ester bond; or 
         R 6  to R 8  are bonded to form a cyclic structure; 
         X represents CH 2 , C(CH 3 ) 2  or an oxygen atom; 
         R 16  mutually independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a sulfonic acid group, a cyano group, a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond, an ester bond or a sulfonyl group; 
         l is an integer between 0 and 2; and 
         m is an integer between 0 and 5. 
       
     
     
       6. A salt represented by general formula (12), 
       
         
           
           
               
               
           
         
         wherein A represents a monovalent organic group represented by general formula (8): 
       
       
         
           
           
               
               
           
         
         wherein R 9  to R 15  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond or an ester bond; 
         X represents CH 2 , C(CH 3 ) 2  or an oxygen atom; 
         Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms; 
         Y represents a single bond or a substituted or unsubstituted C 1 -C 4  linear alkylene group, a substituted or unsubstituted C 3 -C 4  branched alkylene group, or a substituted or unsubstituted C 3 -C 4  cyclic alkylene group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group comprises an ether bond or an ester bond; and 
         M represents an alkali metal ion or an ammonium ion. 
       
     
     
       7. A polymer comprising a repeating unit having a bis(perfluoroalkanesulfonyl)methyl group and selected from the group consisting of general formula (8-A), general formula (8-B) and general formula (8-C): 
       
         
           
           
               
               
           
         
         wherein Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms, 
         R 13  to R 15  mutually independently represent a hydrogen atom or a substituted or unsubstituted C 1 -C 12  linear alkyl group, a substituted or unsubstituted C 3 -C 12  branched alkyl group, a substituted or unsubstituted C 3 -C 12  cyclic alkyl group, or a substituted or unsubstituted C 6 -C 12  aryl group, 
         wherein one or more hydrogen atoms in any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 12  linear alkyl group, substituted C 3 -C 12  branched alkyl group, substituted C 3 -C 12  cyclic alkyl group, and substituted C 6 -C 12  aryl group comprises an ether bond or an ester bond, 
         X represents CH 2 , C(CH 3 ) 2  or an oxygen atom, 
         Y represents a single bond or a substituted or unsubstituted C 1 -C 4  linear alkylene group, a substituted or unsubstituted C 3 -C 4  branched alkylene group, or a substituted or unsubstituted C 3 -C 4  cyclic alkylene group, 
         wherein one or more of the hydrogen atoms in any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group is replaced by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and 
         wherein any of the substituted C 1 -C 4  linear alkylene group, substituted C 3 -C 4  branched alkylene group, and substituted C 3 -C 4  cyclic alkylene group comprises an ether bond or an ester bond; and 
         an asterisk “*” represents a bonding hand. 
       
     
     
       8. A solid electrolyte membrane comprising a polymer as claimed in  claim 7 . 
     
     
       9. A membrane electrode assembly for fuel cells, comprising a solid electrolyte membrane as claimed in  claim 8 . 
     
     
       10. A polymer electrolyte fuel cell comprising a solid electrolyte membrane as claimed in  claim 8 . 
     
     
       11. A direct methanol fuel cell comprising a solid electrolyte membrane as claimed in  claim 8 .